Despite the potential application of uranyl-organic coordination polymers (UOCPs) in detecting metal cations and radiation rays, their luminescence properties have not been sufficiently studied at the molecular level. Herein, we synthesized a series of UOCPs (UOCP1-9) with new construction based on bipyridinium salts and diverse auxiliary ligands. The physicochemical properties of the complexes with high purity were systematically characterized, especially the luminescence spectra. A deep theoretical investigation was conducted to illustrate the relation between uranyl coordination and the luminescence spectral property. The results show that the influence of ligand type on the uranyl luminescent spectral properties increases in the order of hydroxide > oxalate > aromatic carboxylate, which can be attributed to the magnitude of orbital interaction between uranyl and ligand. This work helps to profoundly understand uranyl optical properties and electronic structure at the molecular level, providing important hints for recognizing the nature of luminescent spectral features of uranyl-containing materials, as well as the fundamental chemistry of actinide elements.